n‐Bu₄NI/K₂S₂O₈ Mediated Csp²−Csp² Bond Cleavage – Transformylation from p‐Anisaldehyde to Primary Amides

Abstract

n‐Bu4NI/K2S2O8 mediated transformylation from p‐anisaldehyde to primary amides is reported. The mechanistic studies suggest the reaction occurs via a single electron transfer pathway. Based on the DFT electronic structure calculations of various reaction pathways, the most plausible mechanism involves the formation of a phenyl radical cation and an arenium ion as the key intermediates. It represents the first example that p‐anisaldehyde is employed as a formyl source via a non‐metal mediated Csp2‐Csp2 bond cleavage.

n‐Bu4NI/K2S2O8‐Mediated C−N Coupling Between Aldehydes and Amides

“…Among all the aryl aldehydes examined, p-anisaldehyde afforded the highest yield of 2. [15] In the cases where the transformylation products were obtained in low yields, the unreacted amides were recovered. At the same time, the rest of the aldehydes were oxidized to the corresponding carboxylic acids.…”